Organosilyl and organosiloxanyl derivatives of glycerin ethers and their use

ABSTRACT

The invention relates to novel organosilyl and organosiloxanyl derivatives of glycerin ethers of the general formula ##STR1## wherein R represents --OH or the --OCH 2  --CH═CH--(CH 2 ) 3  --CH═CH 2  group or the --(R 5 ) a  --R 6  group or the --OCH 2  --CH═CH--(CH 2 ) 5  --R 4  group.

FIELD OF INVENTION

The invention relates to novel organosilyl and organosiloxanylderivatives of glycerin ethers. The invention further relates tosurfactants in aqueous media comprising an effective amount of theinventive organosilyl and organosiloxanyl derivatives.

OBJECT OF THE INVENTION

An object of the invention is the inventive organosilyl andorganosiloxanyl derivatives of glycerin ethers. A further object of theinvention is a surfactant in aqueous media comprising an effectiveamount of the inventive organosilyl and organosiloxanyl derivatives.

SUMMARY OF THE INVENTION

The inventive derivatives have the general formula ##STR2## wherein Rrepresents --OH, or the --OCH₂ --CH═CH--(CH₂)₃ --CH═CH₂ group, or the--(R⁵)_(a) --R⁶ group, or the --OCH₂ --CH═CH--(CH₂)₅ --R₄ group,

with the proviso that at least one of the R groups has thelast-mentioned meaning,

R⁴ being a silyl group having the formula --SiR¹ R² R³, in which R¹, R²and R³ are the same or different aliphatic or aromatic hydrocarbongroups, or a linear or branched organosiloxanyl group with 2 to 200silicon atoms,

R⁵ is a group having the formula -O(CH₂)_(b) -- or a polyether grouphaving the formula --(OC_(n) H_(2n))_(c), wherein b has a value of 1 to11, n has an average value of 2 to 2.5 and c a value of 1 to 21,

R⁶ is an --OSO₃ X or --OR⁷ group, wherein X is hydrogen, alkali or anoptionally substituted ammonium ion and R⁷ is a hydrogen group, an alkylgroup with 1 to 4 carbon atoms or an acetyl group, and

a is 0 or 1, and is 1 in the event that R⁶ is the --OR⁷ group.

Preferably, R¹, R² and R³ or the organic groups of the polysiloxane arealkyl groups with 1 to 4 carbon atoms and one of these groups can bereplaced by a phenyl group. Particularly preferred are compounds, inwhich at least 90% of the R¹, R² and R³ groups or the organic group ofthe polysiloxane are methyl groups.

The inventive organosilyl or organosiloxanyl derivatives are easilyaccessible by way of the glycerin octadienyl ethers, which are obtainedby telomerizing butadiene with glycerin (Gruber et al., "Chemistry andProperties of Glycerin Ether Sulfates", Tenside Surf Det., 30, (1993),6).

They can be synthesized easily by means of an addition reaction betweensilanes of the general formula ##STR3## or hydrogensiloxanes andglycerin octadienyl ethers of the general formula ##STR4## wherein R is--OH or the --OCH₂ --CH═CH--(CH₂)₃ --CH═CH₂ group, in the presence of aknown hydrosilylation catalyst.

In the event that triethers are used as starting material, compounds ofthe following general formulas ##STR5## or their stereoisomers are thusobtained, wherein R⁴ has the meaning given above.

The above compounds, particularly those with a single silyl or siloxylgroup (formula II), can be used as modifiers for curable resins, such asorganopolysiloxane acrylates, since this novel class of substancescombines the properties of pure organosilicon compounds in anadvantageous manner with those of compounds having strictly ahydrocarbon backbone.

Particularly when used in polymer preparations that consist of two ormore polymers of different types, these modifiers act ascompatibilizers.

In the case that monoethers or diethers are used as starting compound,compounds of the general formula ##STR6## or their stereoisomers areobtained.

Compounds of formula V can also be used over the existing double bondfor modifying the properties of curable resins.

Moreover, the olefinic double bond permits this class of substances tobe used in standard reactions of organic chemistry, such assulfonations, epoxidations, metatheses, brominations, conversions intoBunte salts, etc.

Because of the OH groups, both groups of compounds can also be used asmonohydric or dihydric components for modifying polyester orpolyurethane resins.

The compounds of formulas V and VI are particularly suitable for beingreacted further to surfactant compounds of the general formulas ##STR7##wherein R⁵ and R⁶ have the meaning given above.

The --(R⁵)_(a) --R⁶ group should be selected by a suitable adjustment ofthe HLB value so that the resulting compounds have a high degree ofcompatibility with the target medium. For aqueous media, for example,the HLB should be adjusted to a value greater than 5 by incorporatingsuitable hydrophilic groups.

Preferably, R⁵ is a polyether group having the formula --(OC_(n)H_(2n))_(c) --, in which n preferably has a value of 2.0, so that inthis case all oxyalkylene units are present as oxyethylene units.Subscript c preferably is 3 to 6.

The compounds of formulas VII and VIII can be synthesized by knownmethods by etherifying or alkoxylating the compounds of formulas VI andVII or by sulfonating or sulfating the hydroxyl group, directly linkedto the glycidyl group. The hydroxy-functional polyethers, which resultfrom the etherification or alkoxylation, can be sulfated subsequently.The group, joined on during the sulfation, is the --OSO₃ X group,wherein X is hydrogen, alkali or an optionally substituted ammonium ion.

Examples of the inventive organosilyl or organosiloxanyl derivatives ofglycerin ethers with surfactant character are ##STR8##

A further object of the invention is the surfactants in aqueous mediacomprising the effective amount of the compounds of the general formulasVII and VIII. Important utilizations of the compounds as surfactantsare:

as wetting agent: in preparations for treating plants (agriculturalformulations); for improving the wetting of low surface energysubstrates, such as polyethylene and polypropylene surfaces, for use inthe paint industry; in the manufacture of photographic films; inelectroplating;

as dispersant for dispersion paints, pigments and fillers;

as emulsifiers or additives in the textile industry for producingtextile auxiliaries, finishes, lubricants and antistatic preparations;as dyeing aids;

as surfactants in general: for use in fire extinguishers, as foamstabilizers; as surface active additives in high-speed printing inks,adhesives, dispersion adhesives, melt adhesives; for use in detergents;as additives for industrial cleaners;

as raw materials for use in cosmetics, such as in personal careproducts, shampoos, shower baths;

in industrial applications and in the household: as anti-fogging agents;for use in dish-rinsing detergents, laundry detergents, toilet cleaners,self-gloss emulsions.

In this connection, the incorporation of organosilane and, particularly,of trimethylsilane groups, provides, contrary to structures withimmanent siloxane substitution at the glycerin backbone, the option ofachieving biologically degradable surfactants.

EXAMPLE 1 Addition Reaction Between Trimethylsilane and GlycerinMonooctadienyl Ether

Into a 300 mL laboratory autoclave, 35.0 g (0.175 moles) of glycerinmonooctadienyl ether, 0.5 g of sodium carbonate and 3 mg ofcis-(diamino)dichloroplatinum are weighed. In an inert atmosphere ofargon, the autoclave and contents are cooled in an acetone/dry ice bathand 13.6 g (0.184 moles) of trimethylsilane, with a boiling point of6.7° C. are siphoned over from the condensed phase. The autoclave isclosed and heated to 130° C. At the same time, the internal pressureincreases to 12.3 bar, only to fall once again then to 4.5 bar, whichindicates a reaction.

After the autoclave is cooled to room temperature and the pressure inthe autoclave is relieved, the contents, weighing 46.5 g (this indicatesa mass loss of 1.5 g) are freed from platinum catalyst by filtration.

Hydroxyl number: 409 (theoretical), 385 (actual)

The ²⁹ Si-NMR and ¹ H-NMR spectroscopic analyses reveals the followingstructure for the product: ##STR9## The product is freed from volatilecomponents at 50° C. under the vacuum of an oil pump and then usedwithout further preparation for the ethoxylation.

EXAMPLE 2 Use of the Addition-Reaction Product Obtained in Example 1 forEthoxylation

To a 3-neck flask, which is equipped with an intensive condenser,thermometer, dropping funnel provided with a cooling mantle and anitrogen connection, 40 g (0.145 moles) of the addition-reaction productof Example 1 and 1 g of a 50% boron trifluoride etherate solution areadded. After that, 56.5 g (1.28 moles) of condensed ethylene oxide isslowly added dropwise. The exothermic reaction is counteracted by usingan ice bath, so that the internal temperature does not exceed 20° to 30°C. After that, stirring is continued for a further 2 hours at roomtemperature and the reaction solution is neutralized with 2 g of sodiumhydrogen carbonate and 1 g of water (1% by weight). Subsequently, thevolatile components are removed from the product at 90° C. under thevacuum of a water-jet pump.

The subsequent filtration after prior addition of filter aid "Celite J10" results in a clear product, which is slightly colored yellow and,according to ¹ H-NMR spectroscopy as well as GPC, has 4 units ofoxyalkylene and, accordingly, can be reproduced by the following averageformula: ##STR10##

EXAMPLE 3 Synthesis of the Product of the Addition Reaction BetweenGlycerin Dioctadienyl Ether and Two Equivalents ofHeptamethyltrisiloxane

To a 500 mL 4-neck flask with KPG stirrer and reflux condenser, 70 g(0.23 moles) of glycerin dioctadienyl ether together with 10 mg ofcis-diaminoplatinum dichloride are added with stirring and heated to100° C. Heptamethyltrisiloxane (102 g, 0.46 moles) is successively addeddropwise. At the end of the addition (about 1 hour), stirring iscontinued for a further 2 hours at 120° C. After the reaction batch hascooled down, catalyst is removed by means of a filter press.

A readily mobile, colorless oil (165 g) is obtained, the structure ofwhich was characterized by ¹ H-NMR as follows: ##STR11##

EXAMPLE 4 Use of the Product Obtained in Example 3 for Synthesizing itsIsopropylammoniumsulfato Derivative

To a 500 mL 4-neck flask, equipped with stirrer, reflux condenser,thermometer and dropping funnel, 150 g (0.20 moles) of theaddition-reaction product from Example 3, 20.4 g (0.21 moles) of freshlyground (mortar and pestle) amidosulfuric acid and 20 g ofdimethylformamide are mixed under a blanket of nitrogen and heated for 4hours to an internal temperature of 85° C. The reaction mixture isthereupon mixed at room temperature with 14.2 g (0.24 moles) ofi-propylamine, the temperature of the mixture increasing and ammonia gasescaping. By these means, acid groups present in the product areneutralized at the same time. After that, the product is filtered andthen freed from N,N-dimethylformamide and excess isopropylamine at 85°C. under the vacuum of an oil pump.

A highly viscous, yellowish oil (174 g) is obtained.

The integration relationship in the ¹ H-NMR spectrum confirms a degreeof sulfation of 85% and assigns the following structure to the product:##STR12##

We claim:
 1. Organosilyl and organosiloxanyl derivatives of glycerinethers of the general formulawherein R represents --OH, --OCH₂--CH═CH--(CH₂)₃ --CH═CH₂ group, --(R⁵)_(a) --R⁶ group or --OCH₂--CH═CH--(CH₂)₅ --R₄ group,with the proviso that at least one of the Rgroups has the last-mentioned meaning, R⁴ being a silyl group having theformula --SiR¹ R² R³, in which R¹, R² and R³ are the same or differentaliphatic or aromatic hydrocarbon groups, or a linear or branchedorganosiloxanyl group with 2 to 200 silicon atoms, R⁵ is a group havingthe formula -O(CH₂)_(b) -- or a polyether group having the formula--(OC_(n) H_(2n))_(c), wherein b has a value of 1 to 11, n has anaverage value of 2 to 2.5 and c a value of 1 to 2, R⁶ is an --OSO₃ X or--OR⁷ group, wherein X is hydrogen, alkali or an substituted ammoniumion which may be substituted and R⁷ is a hydrogen group, an alkyl groupwith 1 to 4 carbon atoms, or an acetyl group, and a is 0 or 1, and is 1in the event that R⁶ is the --OR⁷ group.
 2. The organosilyl andorganosiloxanyl derivatives of claim 1, wherein R¹, R² and R³ and theorganic groups of the polysiloxane are alkyl groups with 1 to 4 carbonatoms and one of these groups is a phenyl group.
 3. The organosilyl andorganosiloxanyl derivatives of claim 2, wherein at least 90% of the R¹,R² and R³ groups and the organic groups of the polysiloxane are methylgroups.
 4. The organosilyl and organosiloxanyl derivatives of claim 1 or2, wherein one or two of the R groups represent the --(R⁵)_(a) --R⁶group.
 5. The organosilyl and organosiloxanyl derivatives of claim 4,wherein R⁵ is a polyether group, in which n has a value of 2 and c avalue of 3 to
 6. 6. The organosilyl and organosiloxanyl derivatives ofclaim 4, wherein X is an alkylammonium group, the alkyl group of whichhas 1 to 10 carbon atoms.
 7. The organosilyl and organosiloxanylderivatives of claim 1 or 2, wherein two of the R groups represent the--OCH₂ --CH═CH--(CH₂)₃ --CH═CH₂ group.
 8. A surfactant in aqueous mediacomprising an effective amount of the organosilyl and organosiloxanylderivatives of the glycerin ethers of claims 4, 5 or 6.